CN106920917A - A kind of preparation method of electrode slurry - Google Patents
A kind of preparation method of electrode slurry Download PDFInfo
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- CN106920917A CN106920917A CN201510999403.6A CN201510999403A CN106920917A CN 106920917 A CN106920917 A CN 106920917A CN 201510999403 A CN201510999403 A CN 201510999403A CN 106920917 A CN106920917 A CN 106920917A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a kind of preparation method of electrode slurry, including：The monomer of active material, binding agent is mixed with polymerization initiator, polymerisation is carried out, lithium ion battery negative material is obtained.Compared with prior art, the present invention mixes the monomer of binding agent with active material, the monomer of binding agent can form uniform ionic atmosphere in surface of active material, make these monomers that polymerisation to occur by the method for in-situ polymerization again, form the binding agent of long-chain molecule and stably and firmly can form active force with active material, and then the structural stability of active material in electrode can be improved, so as to improve the cyclical stability of electrode.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of preparation method of electrode slurry.
Background technology
Lithium ion battery as new generation of green rechargeable secondary cell, with voltage it is high, energy density is big,
Self discharge is small, good cycle the characteristics of, occupy very important status in the modern digital epoch.With
The development in epoch, people are to high-energy long circulating lithium battery requirement more and more higher.
Lithium ion battery is by positive electrode, negative material, barrier film, electrolyte, collector, lug, outer
The part such as shell is constituted, wherein mainly the part of influence battery capacity and energy is the both positive and negative polarity material of battery
Material, and it is the metallic crystal oxidation of transition metal (Co, Ni, Mn, Fe) composition that positive electrode is most of
Thing, due to being limited by lattice structure, the gram volume of positive electrode is limited by larger.At present commercially
The lithium ion battery that change is used mainly uses graphite as negative material, but due to the theoretical specific capacity of graphite
Amount is only 372mAh/g, and so low capacity is difficult to meet the demand in various markets.Accordingly, it would be desirable to study
A kind of new negative active core-shell material with more height ratio capacity improves the performance of lithium ion battery, to meet
The demand in market.
Silicon (Si) as a kind of novel anode material, due to silicon lithium alloy can be formed in silicon embedding lithium state completely
(Si+4.4e-+4.4Li+→ Li4.4Si), it has theoretical capacity 4200mAh/g and intercalation potential low (small
In 0.5V)) the advantages of, its gram volume exceedes ten times of current commodity graphite.Also, silicon is in the earth's crust
Content be only second to oxygen (O), account for the 26.4% of gross mass, therefore silicon in lithium ion battery negative material
In have very big application prospect.
However, the physicochemical characteristics due to silicon materials in itself, when for lithium ion battery negative material
There is also some problems：First, the electronic conductivity of silicon materials is less than graphite material, and in normal condition
Under, silicon face can have one layer of thin earth silicon material again；Secondly, silicon has during removal lithium embedded
There is obvious bulk effect, under completely embedding lithium state, the volume of silicon can expand 300%, due to silicon volume
Significant change can produce larger mechanical stress, cause the circulating battery for doing negative active core-shell material using silicon steady
Qualitative poor, these problems seriously limit application of the silicium cathode material in lithium ion battery.
The first step is to be mixed plurality of raw materials in current lithium ion battery production process, including work
Property material, conductive agent, binding agent and thickener.Binding agent is generally long chain macromolecule material, in mixing
In slurry process, because macromolecule end of the chain active group has electrostatic force from each other, thus in original
In material mixed process, end of the chain inside more long can reunite, it is more difficult to form uniform active force with silicon grain.
Due to the uneven cementation power of silicon face, in its charge and discharge process, volumetric expansion can aggravate particle
With the contact of adjacent material, and silicon materials once lose and can cause it with the good contact of adjacent material
Lose electron channel and inactivate, can further deteriorate the capacity attenuation of silicium cathode material.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of cycle performance to be preferably electrolysed
The preparation method of slurry.
The invention provides a kind of preparation method of electrode slurry, including：
The monomer of active material, binding agent is mixed with polymerization initiator, polymerisation is carried out, lithium is obtained
Ion battery cathode material.
Preferably, the active material be selected from silicon materials, carbon material, tin-based material, metal alloy compositions,
One or more in cobalt acid lithium, LiMn2O4, LiFePO4 and lithium nickelate.
Preferably, the active material includes silicon materials and carbon material；The matter of the silicon materials and carbon material
Amount is than being (30~100)：(70~0).
Preferably, it is additionally added thickener.
Preferably, the thickener is selected from alginic acid, sodium alginate, carboxymethylcellulose calcium, carboxymethyl fibre
One or more in the plain sodium of dimension, polyacrylic acid and Sodium Polyacrylate.
Preferably, the thickener and the mass ratio of active material are (0.001~20)：(100~80).
Preferably, the monomer of the binding agent and the mass ratio of active material are (1~80)：(99~20).
Preferably, the polymerization initiator and the mass ratio of the monomer of binding agent are (0.00001~0.1)：1.
Preferably, the average grain diameter of the active material is 5nm~50 μm.
Present invention also offers a kind of lithium ion battery, including prepared by claim 1~9 any one
Electrode slurry.
The invention provides a kind of preparation method of electrode slurry, including：By active material, binding agent
Monomer mixes with polymerization initiator, carries out polymerisation, obtains lithium ion battery negative material.With it is existing
Technology is compared, and the present invention mixes the monomer of binding agent with active material, and the monomer of binding agent can be in work
Property material surface forms uniform ionic atmosphere, then these monomers is polymerized by the method for in-situ polymerization
Reaction, forms the binding agent of long-chain molecule and stably and firmly can form active force with active material, enters
And the structural stability of active material in electrode can be improved, so as to improve the cyclical stability of electrode.
Experiment shows, lithium ion battery prepared by the electrode slurry prepared using the present invention irreversible appearance first
It is 75% to measure, and 100 weeks capability retentions of circulating battery are 80%.
Brief description of the drawings
Fig. 1 is the preparation flow figure of the embodiment of the present invention 1；
Fig. 2 is the preparation flow schematic diagram of the embodiment of the present invention 1；
Fig. 3 is the preparation process schematic diagram of the embodiment of the present invention 1；
Fig. 4 is that acrylic acid in the embodiment of the present invention 1 and thickener produce the original of chemical bond on silicon materials surface
Reason figure；
Fig. 5 is the stereoscan photograph of silicon materials in the embodiment of the present invention 1；
Fig. 6 is the stereoscan photograph of the active material after the ball milling that obtains in the embodiment of the present invention 1；
Fig. 7 is the stereoscan photograph of lithium ion battery cathode slurry obtained in the embodiment of the present invention 1；
Fig. 8 is that negative electrode is assembled into the structure chart of half-cell in the embodiment of the present invention 1；
Fig. 9 is the first charge-discharge curve map of button cell CR2032 obtained in the embodiment of the present invention 1；
Figure 10 is the cyclic curve figure of button cell CR2032 obtained in the embodiment of the present invention 1；
Figure 11 is the preparation flow figure of comparative example 1；
Figure 12 is the first charge-discharge curve map of button cell CR2032 obtained in comparative example 1；
Figure 13 is the cyclic curve figure of button cell CR2032 obtained in comparative example 1；
Figure 14 is the first charge-discharge curve map of button cell CR2032 obtained in the embodiment of the present invention 4；
Figure 15 is the cyclic curve figure of button cell CR2032 obtained in the embodiment of the present invention 4；
Figure 16 is the cyclic curve figure of button cell CR2032 obtained in the embodiment of the present invention 5.
Specific embodiment
Below in conjunction with the accompanying drawing of the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clearly
Chu, it is fully described by, it is clear that described embodiment is only a part of embodiment of the invention, without
It is whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, belongs to the scope of protection of the invention.
The invention provides a kind of preparation method of electrode slurry, including：By active material, binding agent
Monomer mixes with polymerization initiator, carries out polymerisation, obtains lithium ion battery negative material.
Wherein, the present invention is not particularly limited to the source of all raw materials, is commercially available.
The average grain diameter of the active material is preferably 5nm~50 μm, more preferably 10nm~50 μm,
It is further preferably 10nm~20 μm；The active material for it is well known to those skilled in the art can be as electrode just
The active material of pole can have no special limitation as the active material of Electrode Negative, the present invention
In be preferably silicon materials, carbon material, tin-based material, metal alloy compositions, cobalt acid lithium, LiMn2O4, phosphorus
One or more in sour iron lithium and lithium nickelate, more preferably including silicon materials and carbon material.
The silicon materials are silicon materials well known to those skilled in the art, have no special limitation, this
Micron and/or nano-scale particle shape and/or wire silicon materials, more preferably its average grain diameter are preferably in invention
It is 10nm~50 μm, more preferably 10nm~20 μm；The silicon materials be preferably monocrystalline silicon, polysilicon,
One or more in non-crystalline silicon, the sub- silicon of oxidation, silicon-base alloy and silicon-carbon composite construction.
The carbon material is carbon material well known to those skilled in the art, has no special limitation, this
Invention is preferably conductive black material, more preferably conductive carbon material, carbon microspheres, irregular carbon ball, carbon
One or more in film, carbon-point, porous carbon, carbon fiber, native graphite and Delanium, then it is excellent
Elect conductive acetylene as black；The particle diameter of the carbon material is preferably 5nm~50 μm, more preferably 5nm~10
μm, it is further preferably 5nm~1 μm, most preferably 5nm~100nm.
The silicon materials are preferably (30~100) with the mass ratio of carbon material：(70~0), more preferably
(30~90)：(70~10), be further preferably (50~90)：(50~10), most preferably (80~90)：
(20~10).
When active material includes silicon materials with carbon material, active material is first preferably carried out into ball milling.Ball milling
Silicon materials can be made to be well mixed with carbon material, carbon material can uniformly be wrapped in the surface of silicon materials.
Then, preferably mix with solvent；The solvent is solvent well known to those skilled in the art,
Special limitation is had no, the present invention is preferably water.
The monomer of binding agent is added, thickener is preferably additionally added, is well mixed.The list of the binding agent
Body is the monomer that can be used to be polymerized to binding agent well known to those skilled in the art, has no special limit
System, is preferably acrylic acid in the present invention；The monomer of the binding agent is preferably with the mass ratio of active material
(1~80)：(99~20), more preferably (5~80)：(95~20), be further preferably (5~60)：
(95~40), be further preferably (5~40)：(95~60), be further preferably (5~20)：(95~80),
Most preferably (5~15)：(95~85)；The thickener is thickener well known to those skilled in the art
, have no special limitation, the present invention be preferably alginic acid, sodium alginate, carboxymethylcellulose calcium,
One or more in sodium carboxymethylcellulose, polyacrylic acid and Sodium Polyacrylate；The thickener and work
The mass ratio of property material is preferably (0.001~20)：(100~80), more preferably (1~20)：(100~80),
It is further preferably (3~15)：(97~85), most preferably (5~10)：(95~90).
It is eventually adding polymerization initiator.The polymerization initiator is free radical well known to those skilled in the art
Initiator, has no special limitation, and the present invention is preferably organic peroxide evocating agent, inorganic mistake
Peroxide initiator, azo-initiator or redox initiator；The organic peroxide evocating agent
Preferably peroxyester, peroxidating (two) carbonic ester, peroxidating two acyl, the alkane of peroxidating two, peroxide
Change one or more in ketone and hydrogen-based peroxide；The inorganic peroxide initiator is preferably over cure
One or more in Barbiturates, more preferably potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate；The idol
Nitrogen class initiator is preferably azo-bis-isobutyrate hydrochloride (AIBA) and/or the isobutyl imidazoline hydrochloric acid of azo two
Salt (AIBI)；Oxidant in the redox initiator be preferably hydrogen peroxide, persulfate with
One or more in hydroperoxides, reducing agent is preferably ferrous salt and/or sulphite；The polymerization
Initiator is preferably (0.00001~0.1) with the mass ratio of the monomer of binding agent：1, more preferably
(0.001~0.1)：1, be further preferably (0.01~0.1)：1.
After adding polymerization initiator, polymerisation is carried out, obtain electrode slurry.The side of the polymerisation
Method is preferably in thermal polymerization, electromagnetism polymerization, Microwave Emulsifier-Free Polymerization method, light polymerization method and infrared polymerization method
One or more.
The present invention mixes the monomer of binding agent with active material, and the monomer of binding agent can be in active material
Surface forms uniform ionic atmosphere, then makes these monomers that polymerisation to occur by the method for in-situ polymerization,
Form the binding agent of long-chain molecule and stably and firmly can form active force with active material, and then can change
The structural stability of active material in kind electrode, so as to improve the cyclical stability of electrode.
It is of the invention directly to polymerize high polymer binder material, the bonding that polymerization is obtained in surface of active material
Agent molecule amount can be adjusted flexibly, according to actual effect, the amount of adjustment polymerizing condition and initiator, if former
In the case that position polymerization is uneven, thickener can be before polymerization added to adjust the viscosity of reaction system, with
More uniform polymerization state is can reach when ensureing that it is polymerized in the original location.
When the active material is negative active core-shell material, binding agent uniformly may be used with the active force of active material
To promote the formation of surface of active material SEI films, cause with electrolyte reaction so as to reduce active material
Irreversible capacity loss, improve first charge-discharge efficiency, and the SEI films for being formed are in cyclic process
In relatively stable presence so that electrolyte does not further participate in the formation of SEI films in the circulating cycle, improves
Capability retention.
Preferably also electrode slurry is coated in metal collector in the present invention, is made electrode；The coating
Method be manual, semi- or fully automated mode well known to those skilled in the art, it is special to have no
Limitation；Preferably colded pressing, cut and dried after coating, you can obtained electrode slice.
The present invention improves pole with the uniform force of binding agent by improving active material during slurry
The Stability Analysis of Structures of active material in piece, to provide a kind of capacity high, low cost, can be commercialized and and lithium
The method of the chemical preparation electrode slurry that battery production technology matches, also, electrode slurry and metal collection
Fluid can form stronger active force, therefore, the negative pole prepared by the method has electric discharge ratio higher
Capacity, first charge-discharge efficiency and good cycle performance.
In order to further illustrate the present invention, a kind of electrode slurry for providing the present invention with reference to embodiments
Preparation method be described in detail.
Reagent used is commercially available in following examples；Silicon materials used are irregular crystalline state in embodiment
Silicon grain shape, granularity is 1~5 μm；Carbon material used is that conductive acetylene is black in embodiment, and particle diameter is 5~100
nm。
Embodiment 1
Silicon materials and carbon material are 90 according to mass ratio by 1.1：10 ratio is uniform using manual mixing,
Ball mill is added to, ball milling pearl is put into, in air atmosphere, with rotating speed as 300rpmh, ball milling 6h is obtained
Active material after to ball milling.
Active material after 1.2 ball millings that will be obtained in 1.1 mixes with deionized water, is subsequently adding thickener
Sodium alginate powder, sodium alginate powder is 5 with the mass ratio of active material：95, mechanical agitation 4h,
Alginic acid is completely dissolved and is well mixed, then add monomer propylene acid solution, active material and third
The mass ratio of olefin(e) acid is 90：10, mechanical agitation 5min so that acrylic acid is uniformly dispersed in the solution, most
After add initiator ammonium persulfate, ammonium persulfate is 10 with acrylic acid mass ratio：100, mechanical agitation
15min so that ammonium persulfate is completely dissolved, being placed in 70 DEG C of baking ovens carries out heating polymerization, solution after 2h
Gluey dope as lithium ion battery cathode slurry is gradually become by turbid solution.
1.3 lithium ion battery cathode slurries that will be obtained in 1.2 are coated uniformly on thickness for 15 μm of Copper Foil collection
On fluid, the initiator and small organic molecule of electrode surface residual are slightly washed off using deionized water, so
Colded pressing with the pressure of 5MPa afterwards, 120 DEG C are placed in vacuum drying oven after cutting and dry 4h, born
Pole electrode slice.
1.4 negative electrodes that will be obtained in 1.3, lithium piece, barrier film and electrolyte are assembled into glove box
Button cell CR2032.
Fig. 1 is the preparation flow figure of embodiment 1.
Fig. 2 is the preparation flow schematic diagram of embodiment 1, and the first step is added to water for ball milling silicon-carbon black in figure
In；Second step is to add monomer propylene acid molecule and thickener in the first step and stir, active material
Material can realize that molecular level is other and uniform mix with the monomer of binding agent；3rd step is to be added in second step
Ammonium persulfate and the schematic diagram after being polymerized, as shown in fig. 7, bonding agent molecule directly in active material
Surface is polymerized, it is possible to achieve the uniform immixture of molecular level, silicon-carbon blacksurface attached one
The uniform high polymer binder of layer, this layer binder plays a part of to protect silicon grain so that buffering silicon material
Expect the Volume Changes in charge and discharge process, the Volume Changes of material will not be produced significantly to negative electrode
Structural change, the preferably change that structure occurs in charge and discharge process of protection silicon grain footpath.
Fig. 3 is the preparation process schematic diagram of embodiment 1, in material whipping process, by chemical reaction
Process realize the mixed process of material, traditional mechanical agitation before changing rotated by high speed
To realize the uniform mixing of material.The mixed process of chemical reaction realizes binding agent and work from molecule rank
Connection function between property material, this active force can as seen from Figure 4, the silica of silicon face
The active force that can exist with the O-C-OH on acrylic acid of Si-O keys, and during acroleic acid polymerization,
When C=C double bonds on acrylic acid are broken and form C-C-C keys, the surface of silicon materials can form one layer point
The long chain of sub- level, and can there is same active force with the silicon grain of surrounding in this long chain,
Can thus form the electrode structure of silicon-polyacrylic acid, then the carbon black by existing high conductivity reality
The mechanical structure of electron channel and stabilization is showed.
The present invention increases the process of chemical reaction to improve material in lithium ion battery negative material preparation process
Expect the uniform performance of mixing.By the monomer of hybrid adhesive in the slurry and realize it is dispersed after, by
Ionic atmosphere can be formed around active material in the nonpolar action of monomer, then by polymerization, will be single
Body small molecule effect double bond fracture mode forms long-chain molecule, these long-chain molecules in surface of active material,
Connection function is realized between active material, to ensure the mechanical strength of active material, the material of this performance
Can in the battery have the ability of preferably resistance material deformation.
Fig. 4 is that acrylic acid in embodiment 1 and thickener produce the schematic diagram of chemical bond on silicon materials surface.
The silicon materials used in 1.1 are analyzed using ESEM, obtain its stereoscan photograph as schemed
Shown in 5.Selected raw material are the inconsistent silicon materials of shape, particle diameter in testing as seen from Figure 5
It is 1~5 μm.
The active material after the ball milling that obtains in 1.1 is analyzed using ESEM, obtains its scanning electricity
Mirror photo is as shown in Figure 6.As seen from Figure 6, after high speed ball milling, carbon material is due to larger table
Face energy, thus can adsorb on silicon materials surface.
The lithium ion battery cathode slurry obtained in 1.2 is analyzed using ESEM, obtains its scanning
Electromicroscopic photograph is as shown in Figure 7.
Fig. 8 is that negative electrode is assembled into the structure chart of half-cell in embodiment 1, and wherein a is negative pole sealing
Lid, b be plastic closure, c be nickel pad, d be negative electricity pole piece, e be barrier film, f be lithium piece,
G is positive pole closure.
Using the button cell CR2032 electrochemistry obtained in LAND series batteries test system and test 1.4
Performance.
Fig. 9 is the first charge-discharge curve map of button cell CR2032 obtained in embodiment 1, first not
Reversible capacity is de- lithium capacity/embedding lithium capacity, as shown in Figure 9 its first irreversible capacity be 75%, by scheming
9 it can be seen that the half-cell that is obtained out of the present invention first can not reverse efficiency will be apparently higher than first in comparative example 1
It is secondary can not reverse efficiency, illustrating the preparation method of lithium ion battery negative material of the present invention can cause silicon materials
With surface state evenly and cementation power.
Figure 10 is the cyclic curve figure of button cell CR2032 obtained in embodiment 1, as shown in Figure 10
100 weeks capability retentions of circulating battery are 80%.The present invention utilizes the side of chemistry polymerizing in situ binding agent
Method, the polymer of acrylic molecules is directly realized by surface of active material, the lithium battery cyclicity produced
Can show excellent, circulation volume conservation rate can be up to 80% within 100 weeks, the chemistry that the present invention is used can be explained
In-situ polymerization has obvious advantage, can effectively improve knot of the silicon materials in electrode charge and discharge process
Structure stability, this stability helps to maintain the ion channel and electron channel in battery, and is unlikely to
Make silicon materials that the result of rupture and electron channel inactivation to occur by Volume Changes repeatedly.
From the above results, the method for being provided according to the present invention can produce the lithium-ion electric of excellent performance
Pole material, and the energy density and first charge-discharge efficiency of lithium battery are greatly improved, and circulate
Performance is also obviously improved.
Result can significantly find out that chemistry polymerizing in situ binding agent can realize that material is stirred from that discussed above
Process to improve the uniformity of material mixing, the cohesive force state for improving surface of active material is carried
Rise the chemical property of lithium ion.
Embodiment 2
Silicon materials and carbon material are 90 according to mass ratio by 2.1：10 ratio mixes with deionized water, hand
Work stirs, and is subsequently adding the matter of thickener sodium alginate powder, sodium alginate powder and active material
Amount is than being 5：95, mechanical agitation 4h, make alginic acid be completely dissolved and be well mixed, and then add list
Body acrylic acid solution, active material is 90 with acrylic acid mass ratio：10, mechanical agitation 5min so that
Acrylic acid is uniformly dispersed in the solution, is eventually adding initiator ammonium persulfate, ammonium persulfate with it is acrylic acid
Mass ratio is 10：100, mechanical agitation 15min so that ammonium persulfate is completely dissolved, are placed in 70 DEG C of bakings
Heating polymerization is carried out in case, solution gradually becomes gluey dope as lithium ion battery by turbid solution after 2h
Cathode size.
2.2 lithium ion battery negative materials that will be obtained in 2.1 are coated uniformly on thickness for 15 μm of Copper Foil collection
On fluid, the initiator and small organic molecule of electrode surface residual are slightly washed off using deionized water, so
Colded pressing with the pressure of 5MPa afterwards, 120 DEG C are placed in vacuum drying oven after cutting and dry 4h, born
Pole electrode.
2.3 negative electrodes that will be obtained in 2.2, lithium piece, barrier film and electrolyte are assembled into glove box
Button cell CR2032.
Embodiment 3
Silicon materials and carbon material are 90 according to mass ratio by 3.1：10 ratio is uniform using manual mixing,
Ball mill is added to, ball milling pearl is put into, in air atmosphere, with rotating speed as 300rpmh, ball milling 6h is obtained
Active material after to ball milling.
Active material after 3.2 ball millings that will be obtained in 3.1 mixes with deionized water, is subsequently adding monomer third
Olefin(e) acid solution, active material is 90 with acrylic acid mass ratio：10, mechanical agitation 5min so that propylene
Acid is uniformly dispersed in the solution, is eventually adding initiator ammonium persulfate, ammonium persulfate and acrylic acid quality
Than being 10：100, mechanical agitation 15min so that ammonium persulfate is completely dissolved, are placed in 70 DEG C of baking ovens
Heating polymerization is carried out, solution gradually becomes gluey dope as lithium ion battery negative by turbid solution after 2h
Slurry.
3.3 lithium ion battery negative materials that will be obtained in 3.2 are coated uniformly on thickness for 15 μm of Copper Foil collection
On fluid, the initiator and small organic molecule of electrode surface residual are slightly washed off using deionized water, so
Colded pressing with the pressure of 5MPa afterwards, 120 DEG C are placed in vacuum drying oven after cutting and dry 4h, born
Pole electrode.
3.4 negative electrodes that will be obtained in 3.3, lithium piece, barrier film and electrolyte are assembled into glove box
Button cell CR2032.
Comparative example 1
1.1 by silicon materials, carbon material, binding agent polyacrylic acid and thickener sodium alginate powder according to quality
Than 75：10：10：5 ratio is dissolved in the water together, and manual mixing is uniform, then mechanical agitation 4h
So that mixture is completely dispersed uniformly, lithium ion battery cathode slurry is obtained.
1.2 lithium ion battery cathode slurries that will be obtained in 1.1 are coated uniformly on thickness for 15 μm of Copper Foil collection
On fluid, then colded pressing with the pressure of 5MPa, 120 DEG C of dryings 4 in vacuum drying oven are placed in after cutting
H, obtains negative electrode.
1.3 negative electrodes that will be obtained in 1.2, lithium piece, barrier film and electrolyte are assembled into glove box
Button cell CR2032.
Figure 11 is the preparation flow figure of comparative example 1, by active material, conductive agent, binding agent and thickener
Dissolve in a solvent simultaneously, then by churned mechanically method so that the group of adhesive surface can be with
Surface of active material forms certain weak bond and binding agent macromolecular chain segment and can enwind powder body material and cause
Active material has certain mechanical performance, and the method does not chemically react in whipping process,
Cause mixture to a certain extent by high-speed stirred solvent again simply by simple physical mixing processes
Realize stepless action.
Using the button cell CR2032 electrochemistry obtained in LAND series batteries test system and test 1.3
Performance.Figure 12 is the first charge-discharge curve map of button cell CR2032 obtained in comparative example 1, by
Figure 12 understand its first irreversible capacity be 53%, the active material in the electrode of comparative example 1 is in embedding lithium shape
Under state, there occurs that the movement of breakage of particles and dystopy obtains portion of material and loses electricity because Volume Changes are larger
Subchannel and without electro-chemical activity.Figure 13 is the circulation of button cell CR2032 obtained in comparative example 1
Curve map, 100 weeks capability retentions of circulating battery are 10% as shown in Figure 13, because silicon materials are in reality
In the application of border, cycle performance is bad, only has former capacity by 100 weeks circulation volume conservation rates in lithium battery
10% or so of value, loop attenuation value declines also very fast.
Embodiment 4
4.1 mix graphite material with deionized water, are subsequently adding thickener sodium alginate powder, alginic acid
Sodium powder end is 5 with the mass ratio of active material：95, mechanical agitation 4h, make alginic acid be completely dissolved and mix
Close uniform, then add monomer propylene acid solution, active material is 90 with acrylic acid mass ratio：10,
Mechanical agitation 5min so that acrylic acid is uniformly dispersed in the solution, is eventually adding initiator ammonium persulfate,
Ammonium persulfate is 10 with acrylic acid mass ratio：100, mechanical agitation 15min so that ammonium persulfate is complete
Dissolving, being placed in 70 DEG C of baking ovens carries out heating polymerization, and solution gradually becomes gluey sticky by turbid solution after 2h
Thing is lithium ion battery cathode slurry.
4.2 lithium ion battery cathode slurries that will be obtained in 4.1 are coated uniformly on thickness for 15 μm of Copper Foil collection
On fluid, the initiator and small organic molecule of electrode surface residual are slightly washed off using deionized water, so
Colded pressing with the pressure of 5MPa afterwards, 120 DEG C are placed in vacuum drying oven after cutting and dry 4h, born
Pole electrode slice.
4.3 negative electrodes that will be obtained in 4.2, lithium piece, barrier film and electrolyte are assembled into glove box
Button cell CR2032.
Using the button cell CR2032 electrochemistry obtained in LAND series batteries test system and test 4.3
Performance.
Figure 14 is the first charge-discharge curve map of button cell CR2032 obtained in embodiment 4, first
Irreversible capacity is de- lithium capacity/embedding lithium capacity, as shown in Figure 14 its first irreversible capacity be 84.87%.
Figure 15 is the cyclic curve figure of button cell CR2032 obtained in embodiment 4, as shown in Figure 15
100 weeks capability retentions of circulating battery are 94.97%.The present invention is using chemistry polymerizing in situ binding agent
Method, the polymer of acrylic molecules is directly realized by surface of active material, the lithium battery circulation produced
Performance is excellent, and circulation volume conservation rate can be up to 94.97% within 100 weeks, the present invention can be explained and uses
Chemistry polymerizing in situ method be applicable to conventional graphite negative pole system, it is possible to obtain the electricity of better performances
Pole.
Embodiment 5
5.1 mix cobalt acid lithium material with deionized water, are subsequently adding thickener sodium alginate powder, marine alga
Sour sodium powder end and the mass ratio of active material are 5：95, mechanical agitation 4h, make alginic acid be completely dissolved simultaneously
It is well mixed, monomer propylene acid solution is then added, active material is 90 with acrylic acid mass ratio：
10, mechanical agitation 5min so that acrylic acid is uniformly dispersed in the solution, are eventually adding initiator persulfuric acid
Ammonium, ammonium persulfate is 10 with acrylic acid mass ratio：100, mechanical agitation 15min so that ammonium persulfate
It is completely dissolved, being placed in 70 DEG C of baking ovens carries out heating polymerization, solution gradually becomes gluey by turbid solution after 2h
Dope is lithium ion battery anode glue size.
5.2 lithium ion battery anode glue sizes that will be obtained in 5.1 are coated uniformly on thickness for 15 μm of Copper Foil collection
On fluid, the initiator and small organic molecule of electrode surface residual are slightly washed off using deionized water, so
Colded pressing with the pressure of 5MPa afterwards, 120 DEG C are placed in vacuum drying oven after cutting and dry 4h, obtained just
Pole electrode slice.
5.3 anode electrodes that will be obtained in 5.2, lithium piece, barrier film and electrolyte are assembled into glove box
Button cell CR2032.
Using the button cell CR2032 electrochemistry obtained in LAND series batteries test system and test 5.3
Performance.
Figure 16 is the cyclic curve figure of button cell CR2032 obtained in embodiment 5, as shown in Figure 16
100 weeks capability retentions of circulating battery are 93.79%.The present invention is using chemistry polymerizing in situ binding agent
Method, the polymer of acrylic molecules is directly realized by surface of active material, the lithium battery circulation produced
Performance is excellent, and circulation volume conservation rate can be up to 93.79% within 100 weeks, the present invention can be explained and uses
Chemistry polymerizing in situ method be applicable to positive pole system, it is also possible to obtain the electrode of better performances.
Claims (10)
1. a kind of preparation method of electrode slurry, it is characterised in that including：
The monomer of active material, binding agent is mixed with polymerization initiator, polymerisation is carried out, lithium is obtained
Ion battery cathode material.
2. preparation method according to claim 1, it is characterised in that the active material is selected from silicon
Material, carbon material, tin-based material, metal alloy compositions, cobalt acid lithium, LiMn2O4, LiFePO4 and nickel
One or more in sour lithium.
3. preparation method according to claim 1, it is characterised in that the active material includes silicon
Material and carbon material；The silicon materials are (30~100) with the mass ratio of carbon material：(70~0).
4. preparation method according to claim 1, it is characterised in that be additionally added thickener.
5. preparation method according to claim 4, it is characterised in that the thickener is selected from marine alga
In acid, sodium alginate, carboxymethylcellulose calcium, sodium carboxymethylcellulose, polyacrylic acid and Sodium Polyacrylate
One or more.
6. preparation method according to claim 4, it is characterised in that the thickener and active material
The mass ratio of material is (0.001~20)：(100~80).
7. preparation method according to claim 1, it is characterised in that the monomer of the binding agent with
The mass ratio of active material is (1~80)：(99~20).
8. preparation method according to claim 1, it is characterised in that the polymerization initiator with it is viscous
The mass ratio for tying the monomer of agent is (0.00001~0.1)：1.
9. preparation method according to claim 1, it is characterised in that the active material it is average
Particle diameter is 5nm~50 μm.
10. a kind of lithium ion battery, it is characterised in that including prepared by claim 1~9 any one
Electrode slurry.
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